EP1517799B1 - Thiouroniumsalz als reversionsverhinderndes mittel in einer vulkanisierbaren kautschukzusammensetzung und auf solch einer zusammensetzung basierender reifen - Google Patents

Thiouroniumsalz als reversionsverhinderndes mittel in einer vulkanisierbaren kautschukzusammensetzung und auf solch einer zusammensetzung basierender reifen Download PDF

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Publication number
EP1517799B1
EP1517799B1 EP03759937A EP03759937A EP1517799B1 EP 1517799 B1 EP1517799 B1 EP 1517799B1 EP 03759937 A EP03759937 A EP 03759937A EP 03759937 A EP03759937 A EP 03759937A EP 1517799 B1 EP1517799 B1 EP 1517799B1
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EP
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Prior art keywords
thiouronium salt
alkyl
chosen
carbon atoms
analogue
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English (en)
French (fr)
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EP1517799A1 (de
Inventor
Christiane Blanchard
Salvatore c/o Michelin Okamoto Tire Corp. PAGANO
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Compagnie Generale des Etablissements Michelin SCA
Michelin Recherche et Technique SA France
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Michelin Recherche et Technique SA Switzerland
Compagnie Generale des Etablissements Michelin SCA
Michelin Recherche et Technique SA France
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles

Definitions

  • the invention relates to vulcanizable elastomeric compositions and in particular to vulcanizable diene rubber compositions for the production of a tire. More particularly, the invention relates to novel anti-reversion agents that can be used in such compositions.
  • the vulcanization of unsaturated elastomers results in a transition to the elastic state of the elastomer mixture which is accompanied by changes in the mechanical properties of the mixture.
  • This vulcanization operates during the cooking of the mixture by the establishment of a network of bridges of sulfur between the different polymeric molecules.
  • the network thus established nevertheless suffers from thermal instability.
  • the heating of the tires during rolling generates thermal stresses of the cooked elastomeric mixtures that compose it.
  • These thermal stresses are the effect of overcuring which, when the temperature of the mixture reaches a value close to the vulcanization temperature, causes a phenomenon of reversion.
  • Reversion is a rupture of the elastomeric network by destruction or shortening of the polysulfurized crosslinking bridges. This breaking of the network causes a drop in modulus and adversely modifies the mechanical properties of the elastomeric mixture.
  • a widely described family of anti-reversion agents is the bismaleimides. Used alone, these compounds are particularly illustrated in the document JP91 / 056544 .
  • the combinations of bismaleimides and other compounds such as other anti-reversion agents or vulcanization accelerators, are the subject of particular documents EP 0 191 931 , US5,328,636 , US 5,616,279 , US 5,736,611 or EP 0 823 453 .
  • Bis-citraconimides have also been described in applications of anti-reversion agents, alone or in combination with other additives, especially in documents WO 92/07904 , US 5,623,007 , US 5,872,188 .
  • Bis-citraconic acid and its derivatives are also mentioned as an agent improving resistance to reversion, in particular in the document US 5,696,188 .
  • Another class of anti-reversion agents consists of bis-succinimides and their derivatives, described in particular in the documents US 5,844,049 and WO 96/20246 .
  • the document JP 94/256573 discloses the use of dithiocarbamate salts to improve resistance to reversion.
  • the document EP 0 832 920 discloses the use of zinc dithiophosphate to improve the thermal stabilization of vulcanizates.
  • poly-thiosulphate or poly-thiosulphonate compounds are described which also make it possible to stabilize the vulcanizates with respect to the reversion phenomenon.
  • the document US 5,736,611 teaches the improvement of rubber composition reversion resistance comprising polyacrylates.
  • Anti-reversion agents are an important research area, particularly in the field of pneumatics for which optimal thermal stability is essential.
  • the tire can indeed endure substantial changes in its mechanical properties without this affecting its performance.
  • the present invention aims to propose new anti-reversion agents used in elastomeric compositions more particularly suitable for the realization of a tire.
  • thiouronium salt means the product of the reaction of a thiourea substituted or not on a hydrocarbon halide.
  • Thiouronium salts are widely described in the literature. In the field of organic chemistry, they are in particular reaction intermediates in the synthesis of mercaptans ( GG Urquart, JW Gates, R. Connor, Org. Synth., Collect. vol.3, p.363, 1954 or Fieser & Fieser, Reagents for organic synthesis, vol 1, 1164 ).
  • the literature also includes the use of thiouronium salts in a wide variety of applications such as textile applications ( SM Burkinshaw, XP Lei, JSDC, vol 106, 307, 1990 ) for example to increase the "colorability" of cotton, industrial applications ( FR 2,331,555 , ANIC SPA) as a trap for heavy metals or acting on the corrosion of steel in an acid medium ( J.Electrochem. Soc.
  • the invention also relates to the use, as an anti-reversion agent in a vulcanizable rubber composition for the manufacture of tires or semi-finished products for the manufacture of tires, of a salt thiouronium or an analogue of this salt, as defined above.
  • Another subject of the invention concerns the use of a rubber composition according to the invention for the manufacture of thermally stabilized rubber articles, in particular tires or semi-finished rubber products intended for these tires, these semi-finished products being chosen in particular from the group constituted by the treads, the sub-layers intended for example to be placed under these treads, the crown reinforcing plies, the sidewalls, the plies of carcass reinforcement, heels, protectors, inner tubes and tubeless tire inner liner.
  • the invention furthermore relates to these tires and these semi-finished products themselves, when they comprise an elastomeric composition according to the invention, these tires being intended to equip, for example, passenger vehicles, 4x4 vehicles. (four-wheel drive), SUV ("Sport Utility Vehicles"), two wheels (including bicycles or motorcycles), such as industrial vehicles chosen from light trucks, "heavy vehicles” - ie, metro, buses, road transport units ( trucks, tractors, trailers), off-the-road vehicles, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
  • passenger vehicles 4x4 vehicles.
  • SUV Sport Utility Vehicles
  • two wheels including bicycles or motorcycles
  • industrial vehicles chosen from light trucks, "heavy vehicles” - ie, metro, buses, road transport units ( trucks, tractors, trailers), off-the-road vehicles, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
  • the invention also relates to a process for reducing the reversion rate of a vulcanized rubber composition for the manufacture of tires or semi-finished products intended for the manufacture of tires, this process being characterized by incorporation into this invention.
  • compositions according to the invention are also suitable for the production of rubber articles other than semi-finished articles for tires, also subject to thermal stresses and which require improved thermal stability to prevent degradation of their properties. mechanical.
  • the rubber compositions according to the invention are based on at least each of the following constituents: (i) at least one diene elastomer, (ii) at least one reinforcing filler and (iii) at least one thiouronium salt specific as that anti-reversion agent.
  • the reinforcing filler consists of all or part of an inorganic or white filler
  • a coupling agent is associated with it in the rubber compositions according to the invention.
  • composition based on means a composition comprising the various constituents and / or the composition resulting from the in situ reaction of these various constituents, some of these constituents being capable of, or destined to react with each other, at least in part, during the various phases of manufacture of the composition, in particular during its vulcanization.
  • elastomer or "diene” rubber is meant in known manner an elastomer derived at least in part (i.e. a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not).
  • diene elastomers can be classified into two categories: "essentially unsaturated” or "essentially saturated”.
  • essentially unsaturated is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%).
  • diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated” diene elastomers. "(low or very low diene origin, always less than 15%).
  • the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
  • diene elastomer any type of diene elastomer
  • one skilled in the art of the tire will understand that the present invention is first used with essentially unsaturated diene elastomers, in particular of the type (a) or ( b) above and more particularly with isoprenic elastomers, in particular with natural rubber (NR).
  • essentially unsaturated diene elastomers in particular of the type (a) or ( b) above and more particularly with isoprenic elastomers, in particular with natural rubber (NR).
  • NR natural rubber
  • conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5 alkyl) -1,3-butadienes, such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
  • 2,3-dimethyl-1,3-butadiene 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl- 1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
  • Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene" mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene and divinylbenzene. vinyl naphthalene.
  • the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinyl aromatic units.
  • the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
  • the elastomers can be for example block, statistical, sequenced, microsequenced, and be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
  • Suitable polybutadienes and in particular those having a content in units -1.2 of between 4% and 80% or those having a content of cis-1,4 greater than 80%, polyisoprenes, butadiene-styrene copolymers and in especially those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a 1,2-butadiene content of the butadiene part of between 4% and 65%, a content of trans-1,4 between 20% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a glass transition temperature (Tg, measured according to ASTM D3418 standard).
  • Tg glass transition temperature
  • the isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg of between -25 ° C and -50 ° C .
  • butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content of between 5% and 50% by weight and more particularly of between 10% and 40%, an isoprene content of between 15% and 60%.
  • the diene elastomer of the composition in accordance with the invention may be chosen from the group of highly unsaturated diene elastomers constituted by the polybutadienes (BR), polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
  • Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers.
  • SBIR butadiene-styrene
  • the diene elastomer is for example an SBR, whether it is an emulsion-prepared SBR ("ESBR") or a solution-prepared SBR ("SSBR "), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), or BR / NR (or BR / IR).
  • SBR emulsion-prepared SBR
  • SSBR solution-prepared SBR
  • an SBR elastomer use is made in particular of an SBR having a styrene content of between 20% and 30% by weight, a vinyl bond content of the butadiene part of between 15% and 65%, a bond content of trans-1,4 between 15% and 75% and a Tg of between -20 ° C and -55 ° C.
  • SBR copolymer preferably prepared in solution (SSBR)
  • SSBR polybutadiene
  • BR polybutadiene
  • the diene elastomer is in particular an isoprene elastomer;
  • isoprene elastomer is understood to mean, in known manner, a homopolymer or copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
  • isoprene copolymers examples include copolymers of isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR).
  • This isoprene elastomer is preferably natural rubber or synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (mol%) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
  • the diene elastomer may also consist, in whole or in part, of another highly unsaturated elastomer such as, for example, an SBR elastomer.
  • the composition in accordance with the invention may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer, which this copolymer is for example used or not in admixture with one or more of the above-mentioned highly unsaturated diene elastomers.
  • the composition in accordance with the invention may contain at least one essentially saturated diene elastomer copolymer type of isobutene and isoprene (butyl rubber), as well as the halogenated versions of these copolymers.
  • compositions of the invention may contain a single diene elastomer or a mixture of several diene elastomers, the diene elastomer (s) may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers. More particularly, the compositions according to the invention contain as diene elastomer at least one isoprene elastomer, in particular natural rubber, alone or as a mixture, predominantly or not, with at least one other diene elastomer.
  • the reinforcing filler used in the context of the present invention may consist of an inorganic or white filler or of an organic filler, for example carbon black, or a mixture of these two types of filler.
  • the reinforcing inorganic filler constitutes the majority, ie more than 50% by weight of the total reinforcing filler, more preferably more than 80% by weight of this total reinforcing filler.
  • the reinforcing inorganic filler is a mineral filler of the silica (SiO 2 ) or alumina (Al 2 O 3 ) type, or a mixture of these two fillers.
  • the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
  • Highly dispersible precipitated silicas are preferred, particularly when the invention is used for the manufacture of tires having a low rolling resistance;
  • highly dispersible silica means in a known manner any silica having a significant ability to deagglomeration and dispersion in an elastomeric matrix, observable in known manner by electron or optical microscopy, thin sections.
  • Such preferred highly dispersible silicas there may be mentioned Perkasil silica KS 430 from Akzo, silica BV3380 from Degussa, silicas Zeosil 1165 MP and 1115 MP from Rhodia, silica Hi-Sil 2000 of the PPG company, the silicas Zeopol 8741 or 8745 of the Huber Company, precipitated precipitated silicas such as for example the "doped" aluminum silicas described in the application EP-A-0 735 088 .
  • the reinforcing alumina used is preferably a highly dispersible alumina having a BET surface area ranging from 30 to 400 m 2 / g, more preferably from 60 to 250 m 2 / g, an average particle size of at most 500 nm, more preferably at most equal to 200 nm, as described in the application EP-A-0 810 258 supra.
  • alumina A125, CR125, D65CR from Baikowski.
  • reinforcing inorganic filler is present indifferent, whether in the form of powder, microbeads, granules or beads.
  • reinforcing inorganic filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible silicas and / or aluminas as described above.
  • the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 60 and 250 m 2 / g. more preferably between 80 and 200 m 2 / g.
  • the reinforcing inorganic filler can also be used in blending (mixing) with carbon black.
  • Suitable carbon blacks are all carbon blacks, especially blacks of the HAF, ISAF, SAF type conventionally used in tires and particularly in treads of tires.
  • blacks mention may be made of N115, N134, N234, N339, N347 and N375 blacks.
  • the amount of carbon black present in the total reinforcing filler can vary within wide limits, this amount of carbon black being preferably less than the amount of reinforcing inorganic filler present in the rubber composition.
  • compositions according to the invention in particular in the treads incorporating such compositions, it is preferable to use, in a small proportion, a carbon black in combination with the reinforcing inorganic filler, at a preferential rate of between 2 and 20%. pce, more preferably in a range of 5 to 15 phr. In the ranges indicated, it benefits from the coloring properties (black pigmentation agent) and anti-UV carbon blacks, without also penalizing the typical performance provided by the reinforcing inorganic filler, namely low hysteresis (decreased rolling resistance) and high adhesion on wet, snowy or icy ground.
  • the total reinforcing filler content is between 10 and 200 phr, more preferably between 20 and 150 phr, the optimum being different according to the applications. targeted; indeed, the level of reinforcement expected on a bicycle tire, for example, is in a known manner much lower than that required on a tire capable of driving at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for commercial vehicles such as Heavy Trucks.
  • the amount of reinforcing inorganic filler is preferably between 30 and 140 phr, more preferably included in a range of 50 to 120 pce.
  • the rubber composition also comprises a coupling agent.
  • Coupling agents (silica / diene elastomer), of variable efficiency, have been described in a very large number of documents and are well known to those skilled in the art. Any known coupling agent that can effectively diene rubber compositions usable for the manufacture of tire treads, the bonding between a reinforcing inorganic filler such as silica and a diene elastomer, in particular organosilanes or polyfunctional polyorganosiloxanes carrying the X 'and Y' functions above.
  • a reinforcing inorganic filler such as silica and a diene elastomer, in particular organosilanes or polyfunctional polyorganosiloxanes carrying the X 'and Y' functions above.
  • Polysulphurized silanes called “symmetrical” or “asymmetrical” silanes according to their particular structure, are used, as described for example in patents or patent applications.
  • polysulphurized silanes mention may be made more particularly of polysulfides (especially disulfides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 alkoxyl) -alkyl (C 1 -C 4 ) silyl-alkyl (C 1 -C 4 )), such as, for example, bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl) polysulfides.
  • polysulfides especially disulfides, trisulphides or tetrasulfides of bis- (C 1 -C 4 alkoxyl) -alkyl (C 1 -C 4 ) silyl-alkyl (C 1 -C 4 )
  • bis- (C 1 -C 4 alkoxyl) -alkyl (C 1 -C 4 ) silyl-alkyl (C 1 -C 4 ) such as, for example, bis (3-
  • TESPT bis (3-tri-ethoxysilylpropyl) tetrasulfide
  • TESPD bis (3-tri-ethoxysilylpropyl) tetrasulfide
  • TESPD bis (3-tri-ethoxysilylpropyl) tetrasulfide
  • TESPD bis (3-tri-ethoxysilylpropyl) tetrasulfide
  • TESPD bis disulfide
  • TESPD is marketed for example by Degussa under the name Si75 (as a mixture of disulfide - 75% by weight - and polysulfides), or by the company Witco under the name Silquest A1589.
  • TESPT is marketed for example by Degussa under the name Si69 (or X50S when it is supported at 50% by weight on carbon black), or by Osi Specialties under the name Silquest A1289 (in both cases). case, commercial mixture of polysulfides with a mean value for n which is close to 4).
  • the coupling agent used could be previously grafted (via the function "X" ') on the diene elastomer of the composition of the invention, the elastomer thus functionalized or "pre-coupled” then having the function "Y" free for the reinforcing inorganic filler.
  • the coupling agent could also be grafted beforehand (via the function "Y” ') on the reinforcing inorganic filler, the thus "pre-coupled” filler can then be bonded to the diene elastomer via the free functions "X” .
  • the coupling agent may optionally be associated with a suitable “coupling activator”, that is to say a body (single compound or combination of compounds) which, mixed with this coupling agent, increases the effectiveness. of the latter (see, for example, WO00 / 5300 and WO00 / 5301 above).
  • a suitable “coupling activator” that is to say a body (single compound or combination of compounds) which, mixed with this coupling agent, increases the effectiveness. of the latter (see, for example, WO00 / 5300 and WO00 / 5301 above).
  • Y is a linear alkylene radical, more particularly an alkylene radical having from 4 to 10 carbon atoms and even more particularly 6 carbon atoms.
  • Rubber compositions comprising such compounds are a preferred embodiment of the invention.
  • the thiouronium salts will be chosen more particularly from the compounds of formula (I) in which R1, R2, R3 and R4, which may be identical or different, designate a hydrogen atom or a group chosen from alkyl radicals. C1-C6, C2-C8 alkenyl.
  • the thiouronium salt analogues of the compounds of formula (I) in which R2 and R3 together with the two nitrogen atoms to which they are bonded will be chosen to form an unsaturated heterocycle of 3 to 5 carbon atoms unconjugated to a benzene ring, R1 and R4 being as defined above.
  • the thiouronium salts and their analogs according to the invention can be obtained by simple conventional methods.
  • a thiourea of formula: R1R2 N - C ( S) -N R3R4, the substituents R1, R2, R3 and R4, which may be identical or different, denoting a hydrogen atom or a monovalent hydrocarbon group, linear or branched, chosen from C1-C6 alkyl, C2-C8 alkenyl and C5 cycloalkyl groups; -C8, aryl, aralkyl the alkyl radical being C1-C6, on a compound of formula X - Y - X, X and Y being as defined above, in a predetermined solvent for a predetermined time.
  • the substitution reaction leads to the formation of a thiouronium salt of formula (I) defined above.
  • the anti-reversion agent is present in the vulcanizable rubber composition according to the invention in proportions ranging from 0.1 to 10 phr, preferably from 0.5 to 5.0 phr.
  • the elastomeric compositions according to the invention generally comprise a sulfur-based vulcanization system.
  • the vulcanization system itself is preferably based on sulfur and a primary vulcanization accelerator, in particular a sulfenamide type accelerator.
  • a primary vulcanization accelerator in particular a sulfenamide type accelerator.
  • various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid, guanidine derivatives (especially diphenylguanidine), etc.
  • Sulfur is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr, for example between 0.5 and 3.0 phr, when the invention is applied to a strip. of tire rolling.
  • the primary vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr, in particular when the invention is applied to a tire tread.
  • the elastomeric compositions according to the invention may also comprise all or part of the usual additives used in rubber compositions intended for the manufacture of a tire, such as, for example, extension oils, plasticizers, protective agents such as as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, adhesion promoters, coupling activators, reinforcing resins, acceptors and / or methylene donors.
  • protective agents such as as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, adhesion promoters, coupling activators, reinforcing resins, acceptors and / or methylene donors.
  • To the silica may also be associated, if necessary, a conventional white charge with little or no reinforcing, for example clay particles, bentonite, talc, chalk, kaolin, used for example in colored tire treads.
  • the elastomeric compositions may also contain, in addition to the coupling agents described above, inorganic filler, comprising, for example, the single function Y ', or more generally, processing aids which can be used in a known manner, by improving the dispersion of the reinforcing inorganic filler in the rubber matrix and lowering the viscosity of the compositions, to improve their ability to implement in the green state;
  • these agents used at a preferential rate of between 0.5 and 3.0 phr, are, for example, alkylalkoxysilanes, in particular alkyltriethoxysilanes, such as 1-octyl-triethoxysilane sold by the company Degussa-Hüls under the name Dynasylan Octeo or 1-hexa-decyl-triethoxysilane sold by the company Degussa-Hüls under the name Si216, polyols, polyethers (for example polyethylene glycols), primary, secondary or
  • compositions are manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes called “non-productive” phase) at high temperature, up to at a maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (sometimes referred to as "productive" phase) at lower temperature, typically lower at 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which the vulcanization system is incorporated; such phases have been described for example in the applications EP 501 227 , EP 735 088 , EP 810 258 , EP 881 252 , WO00 / 05300 or WO00 / 05301 .
  • the first (non-productive) phase is carried out in a single thermomechanical step during which, in a suitable mixer such as a conventional internal mixer, all the necessary basic constituents are first introduced. (diene elastomer, reinforcing filler and coupling agent if necessary), then in a second step, for example after one to two minutes of mixing, any additional coating or processing agents and other various additives, with the exception of of the vulcanization system.
  • a suitable mixer such as a conventional internal mixer
  • any additional coating or processing agents and other various additives with the exception of of the vulcanization system.
  • the apparent density of the reinforcing inorganic filler is low (general case of silicas), it may be advantageous to split its introduction into two or more parts.
  • thermomechanical work step may be added to this internal mixer, after the mixture has fallen and intermediate cooling (cooling temperature preferably below 100 ° C.), in order to subject the compositions to a complementary thermomechanical treatment, in particular to improve still further, the dispersion in the elastomeric matrix of the reinforcing filler and its coupling agent.
  • the total mixing time, in this non-productive phase, is preferably between 2 and 10 minutes.
  • the vulcanization system is then incorporated at low temperature, for example between 30 ° C. and 100 ° C., generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 5 and 15 minutes.
  • the manufacturing process according to the invention is characterized in that at least one thiouronium salt or an analogue of this salt, defined above, is introduced into the mixture during the first phase (non-productive phase) and / or during the second phase (productive phase). It will, however, be preferred to add the thiouronium salt or its analogue during the second phase with the vulcanization system. Indeed, the addition of the compound of formula (I) during the productive phase makes it possible to further improve the resistance to reversion.
  • the final composition thus obtained can then be calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile used for the manufacture of semi-finished tires such as strips. rolling plies, crown plies, sidewalls, carcass plies, heels, protectors, inner tubes or tubeless tire inner liner.
  • the vulcanization (or firing) may then be carried out in a known manner at a temperature generally of between 130 ° C. and 200 ° C., preferably under pressure, for a sufficient time which may vary, for example, between 5 and 90 min, depending in particular on the firing temperature, the vulcanization system adopted and the vulcanization kinetics of the composition under consideration.
  • the invention relates to the previously described rubber compositions both in the so-called “raw” state (ie before firing) and in the so-called “cooked” or vulcanized state (ie after vulcanization).
  • the compositions according to the invention can be used alone or in a blend (ie, in a mixture) with any other rubber composition, for example, for pneumatic application, with another composition that can be used for the manufacture of a tire.
  • compositions containing a thiouronium salt or a previously illustrated analog as an anti-reversion agent were then prepared, and these compositions were then tested.
  • the procedure for the preparation of the compositions is as follows: 400 cm 3 are introduced into an internal mixer with standard "Banburry" type pallets, filled to 70% and whose initial tank temperature is approximately 60 ° C. the diene elastomer (or the mixture of diene elastomers, if appropriate), a reinforcing filler, the coupling agent, if appropriate, then, after one to two minutes of mixing, the various other ingredients with the exception of vulcanization system and anti-reversion agent. Thermomechanical work (non-productive phase) is then carried out in one step (total mixing time equal to about 7 minutes), until a maximum "falling" temperature of about 150-170 ° C. is reached.
  • the mixture thus obtained is recovered, cooled and then the vulcanization system and the anti-reversion agent according to the invention are added to an external mixer (homofinisher) at 30 ° C., mixing the whole (productive phase) during 3 to 4 minutes on the roller tool.
  • an external mixer homofinisher
  • compositions are then calendered and vulcanized.
  • the rubber compositions are characterized before and after firing as follows.
  • the aim of the reversion measurement is to indirectly access the evolution of the number of sulphide bridges obtained after cooking at the optimum to that obtained for a given time situated beyond the optimum cooking time. (overcooking or prolonged cooking).
  • One way to determine the reversion is to measure the evolution of the modulus at 100% deformation or 300% deformation after a very long cooking time beyond the optimum. It is possible, for example, to use the parameter% ⁇ M100 which corresponds to the evolution of the nominal secant modulus at 100% elongation between the measurement at the optimum of cooking (at 150 ° C. or 180 ° C.) and after prolonged cooking ( 4 h at 150 ° C. or 6 h at 180 ° C.) and which represents the degree of reversion after 4 or 6 hours of prolonged cooking at 150 ° C. or 180 ° C. respectively.
  • parameter% ⁇ M300 which corresponds to the evolution of the nominal secant modulus at 300% elongation between the measurement at the optimum of cooking (at 150 ° C. or 180 ° C.) and after prolonged cooking of 4 ° C. hours at 150 ° C or 6h at 180 ° C, and which represents the rate of reversion after 4 or 6 hours of prolonged cooking at 150 ° C or 180 ° C respectively.
  • compositions (C) formulated in Tables 1a to 1c which, according to the invention, comprise at least one thiouronium salt or an analogue as an anti-reversion agent according to the invention, are compared below with reference compositions ( T) free of anti-reversion agent.
  • composition C1 according to the invention containing, as anti-reversion agent, the thiouronium salt obtained from thiourea, namely Compound 1, was tested.
  • compositions tested correspond to the formulation of Table 1a, the levels of the various products being expressed in phr, or parts by weight per 100 parts by weight of elastomer.
  • Table 2a gives the properties before and after cooking at the optimum at 150 ° C., and after prolonged cooking for 4 hours at 150 ° C.
  • the thermal stability of the mixtures is measured by the evolution of the nominal secant modulus at 100% and at 300% elongation between the measurement at the optimum cooking temperature (at 150 ° C.) and after prolonged cooking for 4 hours (at 150 ° C.). ° C).
  • Table 3a gives the properties of the compositions tested before and after optimum cooking at 180 ° C., and after prolonged cooking for 6 hours at 180 ° C.
  • the thermal stability of the mixtures is measured by the evolution of the nominal secant modulus at 100% and at 300% elongation between the measurement at the optimum cooking temperature (at 150 ° C.) and after a prolonged cooking time of 6 hours (at 180 ° C.). ° C).
  • composition in accordance with the invention, C1 compared to the composition T1 makes it possible to obtain vulcanizates with properties at the optimum of cooking, even at 180 ° C., close to the control.
  • the evolution of nominal secant modules at 100% and 300% elongation between the optimum cooking temperature (at 180 ° C.) and prolonged cooking (6 hours at 180 ° C.) shows the very good thermal stability of the mixture formulated with the thiouronium salt, superior to the control for which this evolution of modules is important.
  • compositions according to the invention were then tested, the anti-reversion agent is obtained from a bisubstituted or tetrasubstituted thiourea, ie compounds 5, 7 and 9.
  • the compositions tested C5, C6, C7 and C9 correspond to the formulation of Table 1b, the levels of the various products being expressed in phr.
  • composition according to the invention was then tested, the anti-reversion agent is obtained from a compound similar to a thiouronium salt, ie the compound 10.
  • the tested composition C10 corresponds to the formulation of Table 1c, the rates of the different products being expressed in pce.
  • composition according to the invention compared to the composition T3, provides a vulcanizates with properties at the optimum cooking at 150 ° C close to the control.
  • the evolution of the nominal secant moduli at 100% and 300% elongation between the optimum of cooking (at 150 ° C.) and prolonged cooking (4h at 150 ° C.) shows the very good thermal stability of the mixture formulated with the compound 10, superior to the witness for which this evolution of modules is important.
  • a thiouronium salt or an analog of such a salt in the presence of sulfur, it is possible to obtain vulcanizates with improved thermal stability compared to a control formulated without anti-reversion agent in that the reversion is substantially diminished.
  • T1 C1 NR 100 100 Carbon Black (2) 35 35 ZnO (3) 5 4 Stearic acid (4) 2 2 Antioxidant (5) 2 2 Sulfur (6) 1.6 1.6 Compound 1 - 2 CBS (7) 0.6 0.6 (1) peptised natural rubber (mixture of leaves and SAR10); (2) N375 carbon black from Cabot or Columbian; (3) zinc oxide or ZnO Red Seal from Umicore; (4) stearin (Pristerene 4931) from Uniqema; (5) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine Santoflex 13 from Flexsys; (6) sulfur of mining origin of the company Siarkopol, oil company Cabrero or synthetic company Solvay; (7) N-cyclohexyl-2-benzothiazol sulfenamide or Santocure CBS from Flexsys.
  • T1 C1 Properties before cooking Mooney (UM) 61 64 Properties after optimum cooking at 150 ° C: M 100 (MPa) 1.53 1.77 M300 (MPa) 1.99 2.13 breaking stress (MPa) 30.2 31.8 elongation rupture (%) 562 566 Properties after prolonged cooking from 4 hours to 150 ° C: M100 (MPa) 1.13 1.69 M300 (MPa) 1.36 2.07 % ⁇ M100 (%) 26 4 % ⁇ M300 (%) 31 3 Composition: T1 C1 Properties after optimum cooking at 180 ° C : M 100 (MPa) 1.18 1.54 M300 (MPa) 1.42 1.87 breaking stress (MPa) 25.4 26.2 elongation rupture (%) 601 555 Properties after prolonged cooking from 6 hours to 180 ° C : M100 (MPa) 0.85 1.34 M300 (MPa) 1 1.54 % ⁇ M100 (%) 29 12 % ⁇ M300 (%) 29 17 Composition N °: T2 C5 C7 C9 NR (1) 100

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Claims (24)

  1. Kautschukzusammensetzung zur Herstellung von Reifen oder Halbzeugen für die Herstellung von Reifen auf Basis von mindestens (i) einem Dienelastomer, (ii) einem verstärkenden Füllstoff und (iii) einem Thiouroniumsalz oder einem Analogon eines Thiouroniumsalzes der folgenden Formel (I):

            A-S-Y-S-A     (I)

    worin
    - A für eine Gruppe
    Figure imgb0022
     die mit einem Molekül HX bzw. einem Ion X- assoziiert ist, steht,
    - X für ein Halogenatom steht und
    - Z für -S-R5 oder
    Figure imgb0023
     steht, worin die Reste R1, R2, R3, R4 und R5 gleich oder verschieden sind und für ein Wasserstoffatom oder eine lineare oder verzweigte einwertige Kohlenwasserstoffgruppe, die unter C1-C6-Alkylgruppen, C2-C8-Alkylengruppen, C5-C8-Cycloalkylgruppen, Arylgruppen und Aralkylgruppen, wobei der Alkylrest C1-C6 ist, ausgewählt ist, stehen
    oder auch R2 und R3 oder R5 und R3 mit den Stickstoffatomen, an die sie gebunden sind, einen ungesättigten Heterocyclus mit 3 bis 5 Kohlenstoffatomen bilden, der gegebenenfalls durch einen oder mehrere C1-C6-Alkylreste substituiert ist und gegebenenfalls mit einem Benzolkern konjugiert ist, und R1 und R4 für Wasserstoff, C1-C6-Alkyl oder C2-C8-Alkenyl stehen;
    - Y für eine zweiwertige Kohlenwasserstoffgruppe steht, die unter Alkylenresten mit 1 bis 20 Kohlenstoffatomen, Cycloalkylenresten mit 6 bis 24 Kohlenstoffatomen, Arylenresten mit 6 bis 18 Kohlenstoffatomen und Aralkylenresten mit 7 bis 25 Kohlenstoffatomen ausgewählt ist, wobei die Alkylenreste linear oder verzweigt sind und durch ein oder mehrere unter O und N ausgewählte Heteroatome unterbrochen sein können.
  2. Zusammensetzung nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass das Thiouroniumsalz oder Analogon eines Thiouroniumsalzes unter den Verbindungen der Formel (I), worin Y für einen linearen Alkylenrest, vorzugsweise einen linearen C4-C10-Alkylenrest, steht, ausgewählt ist.
  3. Kautschukzusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Thiouroniumsalz oder Analogon eines Thiouroniumsalzes unter den Verbindungen der Formel (I), worin
    Z für die Gruppe
    Figure imgb0024
     steht,
    die Substituenten R1, R2, R3 und R4 gleich oder verschieden sind und für ein Wasserstoffatom oder eine lineare oder verzweigte einwertige Kohlenwasserstoffgruppe, die unter C1-C6-Alkylgruppen, C2-C8-Alkylengruppen, C5-C8-Cycloalkylgruppen, Arylgruppen und Aralkylgruppen, wobei der Alkylrest C1-C6 ist, ausgewählt ist, stehen
    oder auch R2 und R3 mit den Stickstoffatomen, an die sie gebunden sind, einen ungesättigten Heterocyclus mit 3 bis 5 Kohlenstoffatomen bilden, der gegebenenfalls durch einen oder mehrere C1-C6-Alkylreste substituiert ist, und R1 und R4 für Wasserstoff, C1-C6-Alkyl oder C2-C8-Alkenyl stehen;
    die Gruppe Y die in Anspruch 1 oder 2 angegebene Bedeutung besitzt,
    ausgewählt ist.
  4. Kautschukzusammensetzung nach Anspruch 3, dadurch gekennzeichnet, dass das Thiouroniumsalz unter den Verbindungen der Formel (I), worin R1, R2, R3 und R4 gleich oder verschieden sind und für ein Wasserstoffatom oder eine unter C1-C6-Alkylresten und C2-C8-Alkenylresten ausgewählte Gruppe stehen, wobei die Gruppe Y die in Anspruch 3 angegebene Bedeutung besitzt, ausgewählt ist.
  5. Kautschukzusammensetzung nach Anspruch 3, dadurch gekennzeichnet, dass das Analogon eines Thiouroniumsalzes unter den Verbindungen der Formel (I), worin die Reste R2 und R3 mit den Stickstoffatomen, an die sie gebunden sind, einen ungesättigten Heterocyclus mit 3 bis 5 Kohlenstoffatomen bilden, der nicht mit einem aromatischen Kern konjugiert ist, wobei R1 und R4 sowie die Gruppe Y die in Anspruch 3 angegebene Bedeutung besitzen, ausgewählt ist.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie 0,1 bis 10 phr mindestens einer Verbindung der Formel (I) umfasst.
  7. Zusammensetzung nach Anspruch 6, dadurch gekennzeichnet, dass sie 0,5 bis 5,0 phr mindestens einer Verbindung der Formel (I) umfasst.
  8. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass der verstärkende Füllstoff (ii) ganz oder teilweise aus einem anorganischen Füllstoff in Assoziation mit einem Kupplungsmittel (iv), das die Bindung zwischen dem anorganischen Füllstoff und dem Elastomer (i) gewährleistet, besteht.
  9. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass das Dienelastomer ganz oder teilweise aus mindestens einem Isoprenelastomer besteht.
  10. Zusammensetzung nach Anspruch 9, dadurch gekennzeichnet, dass es sich bei dem Isoprenelastomer um Naturkautschuk handelt.
  11. Verfahren zur Herstellung einer vulkanisierbaren Kautschukzusammensetzung zur Herstellung von Reifen oder Halbzeugen für die Herstellung von Reifen, bei dem man:
    a) in einem Mischer in ein Elastomer mindestens einen verstärkenden Füllstoff einarbeitet;
    b) das Ganze ein- oder mehrmals thermomechanisch knetet, bis eine Höchsttemperatur zwischen 110°C und 190°C erreicht ist,
    c) das Ganze abkühlt,
    d) dann ein Vulkanisationssystem auf Basis von Schwefel einarbeitet und
    e) das Ganze knetet, bis eine Höchsttemperatur von weniger als 120°C erreicht ist,
    dadurch gekennzeichnet, dass man in mindestens einem der Schritte a) und d) mindestens ein Thiouroniumsalz oder ein Analogon eines Thiouroniumsalzes der Formel (I) gemäß einem der Ansprüche 1 bis 5 einarbeitet.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass man das Thiouroniumsalz oder das Analogon davon in Schritt d) einarbeitet.
  13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass man 0,1 bis 10 phr des Thiouroniumsalzes oder des Analogons davon einarbeitet.
  14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass man 0,5 bis 5,0 phr des Thiouroniumsalzes oder des Analogons davon einarbeitet.
  15. Kautschukgegenstand auf Basis einer Kautschukzusammensetzung nach einem der Ansprüche 1 bis 10.
  16. Kautschukhalbzeug für Reifen auf Basis einer Kautschukzusammensetzung nach einem der Ansprüche 1 bis 10.
  17. Reifen mit einem Kautschukhalbzeug gemäß Anspruch 16.
  18. Verwendung eines Thiouroniumsalzes oder eines Analogons eines Thiouroniumsalzes der folgenden Formel (I):

            A-S-Y-S-A     (I)

    worin
    - A für eine Gruppe
    Figure imgb0025
     die mit einem Molekül HX bzw. einem Ion X- assoziiert ist, steht,
    - X für ein Halogenatom steht und
    - Z für -S-R5 oder
    Figure imgb0026
     steht,
    worin die Reste R1, R2, R3, R4 und R5 gleich oder verschieden sind und für ein Wasserstoffatom oder eine lineare oder verzweigte einwertige Kohlenwasserstoffgruppe, die unter C1-C6-Alkylgruppen, C2-C8-Alkylengruppen, C5-C8-Cycloalkylgruppen, Arylgruppen und Aralkylgruppen, wobei der Alkylrest C1-C6 ist, ausgewählt ist, stehen
    oder auch R2 und R3 oder R5 und R3 mit den Stickstoffatomen, an die sie gebunden sind,
    einen ungesättigten Heterocyclus mit 3 bis 5 Kohlenstoffatomen bilden, der gegebenenfalls durch einen oder mehrere C1-C6-Alkylreste substituiert ist und gegebenenfalls mit einem Benzolkern konjugiert ist, und R1 und R4 für Wasserstoff, C1-C6-Alkyl oder C2-C8-Alkenyl stehen;
    - Y für eine zweiwertige Kohlenwasserstoffgruppe steht, die unter Alkylenresten mit 1 bis 20 Kohlenstoffatomen, Cycloalkylenresten mit 6 bis 24 Kohlenstoffatomen, Arylenresten mit 6 bis 18 Kohlenstoffatomen und Aralkylenresten mit 7 bis 25 Kohlenstoffatomen ausgewählt ist, wobei die Alkylenreste linear oder verzweigt sind und durch ein oder mehrere unter O und N ausgewählte Heteroatome unterbrochen sein können;
    als Reversionsschutzmittel in einer vulkanisierbaren Kautschukzusammensetzung zur Herstellung von Reifen oder Halbzeugen für die Herstellung von Reifen.
  19. Verwendung nach Anspruch 18, dadurch gekennzeichnet, dass das Thiouroniumsalz oder Analogon eines Thiouroniumsalzes unter den Verbindungen der Formel (I), worin Y für einen linearen Alkylenrest, vorzugsweise einen linearen C4-C10-Alkylenrest, steht, ausgewählt ist.
  20. Verwendung nach Anspruch 18 oder 19, dadurch gekennzeichnet, dass das Thiouroniumsalz oder Analogon eines Thiouroniumsalzes unter den Verbindungen der Formel (I), worin
    Z für die Gruppe
    Figure imgb0027
    steht,
    die Substituenten R1, R2, R3 und R4 gleich oder verschieden sind und für ein Wasserstoffatom oder eine lineare oder verzweigte einwertige Kohlenwasserstoffgruppe, die unter C1-C6-Alkylgruppen, C2-C8-Alkylengruppen, C5-C8-Cycloalkylgruppen, Arylgruppen und Aralkylgruppen, wobei der Alkylrest C1-C6 ist, ausgewählt ist, stehen
    oder auch R2 und R3 mit den Stickstoffatomen, an die sie gebunden sind, einen ungesättigten Heterocyclus mit 3 bis 5 Kohlenstoffatomen bilden, der gegebenenfalls durch einen oder mehrere C1-C6-Alkylreste substituiert ist, und R1 und R4 für Wasserstoff, C1-C6-Alkyl oder C2-C8-Alkenyl stehen;
    die Gruppe Y die in Anspruch 19 oder 20 angegebene Bedeutung besitzt,
    ausgewählt ist.
  21. Verwendung nach Anspruch 20, dadurch gekennzeichnet, dass das Thiouroniumsalz unter den Verbindungen der Formel (I), worin R1, R2, R3 und R4 gleich oder verschieden sind und für ein Wasserstoffatom oder eine lineare oder verzweigte einwertige Kohlenwasserstoffgruppe, die unter C1-C6-Alkylgruppen und C2-C8-Alkenylgruppen ausgewählt ist, stehen, wobei die Gruppe Y die in Anspruch 20 angegebene Bedeutung besitzt, ausgewählt ist.
  22. Verwendung nach Anspruch 20, dadurch gekennzeichnet, dass das Analogon eines Thiouroniumsalzes unter den Verbindungen der Formel (I), worin die Reste R2 und R3 mit den Stickstoffatomen, an die sie gebunden sind, einen ungesättigten Heterocyclus mit 3 bis 5 Kohlenstoffatomen bilden, der nicht mit einem Benzolkern konjugiert ist, wobei R1 und R4 sowie die Gruppe Y die in Anspruch 20 angegebene Bedeutung besitzen, ausgewählt ist.
  23. Verfahren zur Verringerung der Reversionsrate in einer vulkanisierten Kautschukzusammensetzung zur Herstellung von Reifen oder Halbzeugen für die Herstellung von Reifen, dadurch gekennzeichnet, dass man in die Kautschukzusammensetzung im Rohzustand durch Kneten mindestens ein Thiouroniumsalz oder ein Analogon eines Thiouroniumsalzes gemäß einem der Ansprüche 18 bis 22 einarbeitet.
  24. Verfahren nach Anspruch 23, dadurch gekennzeichnet, dass man das Thiouroniumsalz oder das Analogon eines Thiouroniumsalzes während der produktiven Phase des Verfahrens zur Herstellung der vulkanisierbaren Kautschukzusammensetzung einarbeitet.
EP03759937A 2002-06-12 2003-06-12 Thiouroniumsalz als reversionsverhinderndes mittel in einer vulkanisierbaren kautschukzusammensetzung und auf solch einer zusammensetzung basierender reifen Expired - Lifetime EP1517799B1 (de)

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FR0207233 2002-06-12
FR0207233A FR2840908B1 (fr) 2002-06-12 2002-06-12 Composition de caoutchouc comprenant un sel de thiouronium, son procede de preparation, pneumatique a base d'une telle composition et utilisation a titre d'agent anti-reversion d'un sel de thiouronium
PCT/EP2003/006160 WO2003106195A1 (fr) 2002-06-12 2003-06-12 Sel de thiouronium a titre d'agent anti-reversion dans une composition de caoutchouc vulcanisable et pneumatique a base d'une telle composition

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